CN114497618A - Zinc-bromine single flow battery structure - Google Patents
Zinc-bromine single flow battery structure Download PDFInfo
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- CN114497618A CN114497618A CN202011262534.3A CN202011262534A CN114497618A CN 114497618 A CN114497618 A CN 114497618A CN 202011262534 A CN202011262534 A CN 202011262534A CN 114497618 A CN114497618 A CN 114497618A
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- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 208000032953 Device battery issue Diseases 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 12
- 238000007599 discharging Methods 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 229940102001 zinc bromide Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0265—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant the reactant or coolant channels having varying cross sections
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
Abstract
The invention relates to a zinc-bromine single flow battery structure, which comprises a single battery or a battery pack formed by connecting more than two single batteries in series, wherein the single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode, wherein the negative electrode frame, the diaphragm and the positive carbon felt electrode are sequentially stacked; the cathode electrode frame is a rectangular flat plate with a middle part provided with a through hole, and a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel are respectively arranged on two opposite sides of the through hole on the surface A on one side of the flat plate; the other two opposite sides of the through hole on the surface A at one side of the flat plate are respectively provided with corresponding opposite flow passages which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow passage; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame. The negative electrode support grid plays a role in supporting the diaphragm, and the situation that the positive electrode carbon felt electrode presses the diaphragm to be in contact with the bipolar plate due to the action of a large pressing force to cause battery failure is avoided.
Description
Technical Field
The invention relates to the technical field of flow battery energy storage, in particular to the field of a zinc bromine single flow battery.
Background
The zinc-bromine single flow battery is a novel flow battery energy storage technology with low cost, high efficiency and long service life, and has the advantages of higher energy density and simple and easy operation. The carbon felt is used as an electrode in the zinc bromine single flow battery, the cost of the carbon felt occupies about 50% of the total cost of the zinc bromine single flow battery, and therefore, the cost of the zinc bromine single flow battery can be greatly reduced by using low-cost electrode materials even without using the electrode. Meanwhile, as the carbon felt material is used as an influencing factor, the nonuniformity of each section of the zinc bromine single flow battery can be caused by the nonuniformity of the carbon felt material, and therefore, the nonuniformity of the zinc bromine single flow battery can be increased by not using the carbon felt in the zinc bromine single flow battery. Since the positive side of the zinc-bromine single flow battery does not flow and the reaction kinetics of bromine are poor, the positive side still needs an electrode with higher reaction activity in order to ensure that the battery has higher efficiency. The cathode of the zinc-bromine single flow battery is the deposition and dissolution of zinc, and the reaction kinetics is better, so that a reaction matrix with higher activity is not required to be relied on; meanwhile, the zinc can be preferentially deposited on the surface of the generated zinc when the zinc is accumulated, and an electrode with more reaction sites is not required to be provided on the negative electrode side, so that the use of a carbon felt material on the negative electrode side of the zinc-bromine single flow battery is extremely feasible. However, the structure that the cathode cavity is adopted and the anode is used for placing the electrode is adopted, the diaphragm is extruded and deformed by the anode electrode due to the fact that the cathode is not supported, reliability of the battery is affected, meanwhile, due to the fact that adhesive force between zinc deposited on the cathode and the bipolar plate is not strong, a zinc simple substance is easily washed away by electrolyte at a high electrolyte flow rate, even a flow channel is blocked, and performance and service life of the battery are affected. Therefore, the addition of a support structure at the negative electrode and the reduction of the flow rate of the electrolyte are the key points of the zinc-bromine single flow battery with the structure that the negative electrode cavity is lifted, and the electrode is placed at the positive electrode.
Disclosure of Invention
The invention provides a zinc-bromine single flow battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the single battery comprises a negative electrode frame, a diaphragm and a positive electrode carbon felt electrode arranged in a through hole in the middle of the positive electrode frame, wherein the negative electrode frame, the diaphragm and the positive electrode carbon felt electrode are sequentially stacked;
the cathode electrode frame is a rectangular flat plate with a through hole in the middle, and a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel, an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, and an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole (namely the surface A where a pair of opposite side edges of the rectangle are positioned, namely the upper side and the lower side of the surface A) on the surface A on one side of the flat plate;
the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame.
The negative electrolyte flows from the negative electrolyte inlet distribution flow channel to the negative electrolyte outlet distribution flow channel in the through hole, and the negative support grid consists of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flow direction of the negative electrolyte (the more than 2 strip-shaped guide plates are sequentially parallel and at intervals from left to right).
The hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 1/3-2/3 of the length of the side edge of the middle through hole parallel to the electrolyte flowing direction.
Meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased.
The widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 2mm-4mm, and the depth of the flow channel is 0.5mm-1 mm; the total thickness of the negative electrode frame is between 1.5mm and 2 mm. The width of the strip-shaped guide plate is 2mm-4mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10mm-15 mm; the thickness of the strip-shaped guide plate is between 1.5mm and 2 mm.
The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) is the same as the thickness of the negative electrode frame. And polar plates or bipolar plates are respectively arranged on two sides of the monocell, and the surfaces of the polar plates or the bipolar plates close to the negative support grids are used as negative reaction sites.
Advantageous effects
(1) The invention provides a zinc-bromine single flow battery structure, which is characterized in that a negative electrode support grid is additionally arranged on a negative electrode, the negative electrode support grid is placed in a negative electrode frame and is in contact with a diaphragm when the battery is assembled, a positive electrode frame is arranged on the other side of the diaphragm, and a positive carbon felt electrode is placed in the positive electrode frame. The negative electrode support grid plays a role in supporting the diaphragm, and the situation that the positive electrode carbon felt electrode presses the diaphragm to be in contact with the bipolar plate due to the action of a large pressing force to cause battery failure is avoided.
(2) According to the structure provided by the invention, the diaphragm has a certain distance from the bipolar plate due to the action of the negative electrode support grid, and the space is enough to enable the negative electrode side of the zinc-bromine single flow battery to deposit more zinc during charging, so that the capacity of the zinc-bromine single flow battery can be effectively improved. In addition, the uniformity of the bipolar plate is obviously better than that of the carbon felt due to the deposition of zinc on the bipolar plate, so that the deposition of zinc is smoother at the initial stage of deposition, and the stability of the zinc-bromine single flow battery is also favorable.
(3) According to the cathode electrode frame structure provided by the invention, the main flow channel adopts a gradually-enlarged flow channel design, the flow area of the main flow channel is gradually increased, the flow speed of electrolyte can be effectively reduced, and the two sides of the electrode frame are additionally provided with 2 opposite flow channels, so that the flow speed of the electrolyte in an electrode reaction area can be further reduced. The reduction of the flow rate of the electrolyte enables the zinc of the zinc cathode to be more stably deposited on the bipolar plate, and the stability and the reliability of the battery are improved.
(4) According to the cathode electrode frame structure provided by the invention, the depth of the cathode flow channel is reduced, so that the overall thickness of the cathode electrode frame is reduced, the conduction path of cathode electrolyte ions is shortened, the internal resistance of the battery is reduced, the volume of the battery is reduced, and the energy density of the battery is improved.
Drawings
Fig. 1 shows a conventional negative electrode frame structure.
Fig. 2 shows a negative electrode frame structure according to the present invention.
Fig. 3 shows a main flow channel of a negative electrode frame according to the present invention.
Fig. 4 negative support grid structure.
Fig. 5 is a charge and discharge performance curve of comparative example 1.
Fig. 6 is a charge and discharge performance curve of comparative example 2.
Fig. 7 is a charge and discharge performance curve of example 1.
Fig. 8 is a charge and discharge performance curve of example 2.
Fig. 9 is a charge/discharge performance curve of example 3.
Fig. 10 is a charge and discharge performance curve of example 4.
Detailed Description
Comparative example 1
Comparative example 1 a zinc-bromine single flow battery was assembled using a conventional structure, with 10 single cells arranged between two collector plates, the single cells comprising a negative electrode frame, a separator, and a positive carbon felt electrode placed in a through hole in the middle of the positive electrode frame, which were stacked in sequence, the negative electrode frame being a rectangular plate with a through hole in the middle, and a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel and the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel and the middle through hole, being provided on opposite sides of the through hole on a surface a on one side of the plate (i.e., on a surface a on which a pair of opposite sides of the rectangle are located, i.e., on the upper and lower sides of the surface a), respectively; the flow channel widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel and the negative electrolyte outlet distribution flow channel are 4mm, and the flow channel depth is 1 mm; the total thickness of the negative electrode frame is 2 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, and the two sides of the monocell are respectively provided with a bipolar plate. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the sections of the galvanic pile and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 8V.
The coulomb efficiency of the charging and discharging of the galvanic pile is 88.2 percent, the voltage efficiency is 76.4 percent, and the energy efficiency is 67.4 percent.
Comparative example 2
Comparative example 2 a zinc-bromine single flow battery was assembled using a conventional structure, with 10 single cells arranged between two collector plates, the single cells comprising a negative electrode frame, a separator, and a positive carbon felt electrode placed in a through hole in the middle of the positive electrode frame, which were stacked in sequence, the negative electrode frame being a rectangular plate with a through hole in the middle, and a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel and the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel and the middle through hole, being provided on opposite sides of the through hole on a surface a on one side of the plate (i.e., on a surface a on which a pair of opposite sides of the rectangle are located, i.e., on the upper and lower sides of the surface a), respectively; the flow channel widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel and the negative electrolyte outlet distribution flow channel are 4mm, and the flow channel depth is 0.5 mm; the total thickness of the negative electrode frame is 1.5 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, and the two sides of the monocell are respectively provided with a bipolar plate. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the electrode stacks and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 8V.
The coulomb efficiency of the charge and discharge of the galvanic pile is 89.1%, the voltage efficiency is 79.4%, and the energy efficiency is 70.7%.
Example 1
Embodiment 1 adopts the zinc-bromine single flow battery structure provided by the present invention, wherein 10 single batteries are arranged between two current collecting plates, each single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode arranged in a through hole in the middle of the positive electrode frame, which are sequentially stacked, the negative electrode frame is a rectangular flat plate with a through hole in the middle, and two opposite sides of the through hole (i.e. surfaces a where a pair of opposite side edges of the rectangle are located, i.e. upper and lower sides of the surface a) on a surface a on one side of the flat plate are respectively provided with a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel with the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel with the middle through hole; the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame. The negative electrode support grid is composed of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flowing direction of the negative electrode electrolyte (more than 2 strip-shaped guide plates are sequentially arranged in parallel and at intervals from left to right). The hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 1/3 with the middle through hole parallel to the side length of the electrolyte flowing direction. Meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased. The widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 4mm, and the depth of the flow channel is 1 mm; the total thickness of the negative electrode frame is 2 mm. The width of the strip-shaped guide plate is 2mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10 mm; the thickness of the strip-shaped guide plate is 2 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) is the same as the thickness of the negative electrode frame. Two sides of the monocell are respectively provided with a bipolar plate, and the surface of the bipolar plate close to the negative support grid is used as a negative reaction site. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the electrode stacks and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 8V.
The coulomb efficiency of the charge and discharge of the galvanic pile is 92.3%, the voltage efficiency is 79.4%, and the energy efficiency is 71.7%.
Example 2
Embodiment 2 adopts the zinc-bromine single flow battery structure provided by the present invention, wherein 10 single batteries are arranged between two current collecting plates, each single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode arranged in a through hole in the middle of the positive electrode frame, which are sequentially stacked, the negative electrode frame is a rectangular flat plate with a through hole in the middle, and two opposite sides of the through hole (i.e., a surface a on which a pair of opposite side edges of the rectangle are located, i.e., upper and lower sides of the surface a) on a surface a on one side of the flat plate are respectively provided with a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel with the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel with the middle through hole; the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame. The negative electrode support grid is composed of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flowing direction of the negative electrode electrolyte (more than 2 strip-shaped guide plates are sequentially arranged in parallel and at intervals from left to right). The hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 1/3 with the middle through hole parallel to the side length of the electrolyte flowing direction. Meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased. The widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 4mm, and the depth of the flow channel is 1 mm; the total thickness of the negative electrode frame is 1.5 mm. The width of the strip-shaped guide plate is 2mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10 mm; the thickness of the strip-shaped guide plate is 1.5 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) is the same as the thickness of the negative electrode frame. Two sides of the monocell are respectively provided with a bipolar plate, and the surface of the bipolar plate close to the negative support grid is used as a negative reaction site. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the electrode stacks and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 8V.
The coulomb efficiency of the charge and discharge of the galvanic pile is 93.6%, the voltage efficiency is 80.1%, and the energy efficiency is 75%.
Example 3
Embodiment 3 adopts the zinc-bromine single flow battery structure provided by the present invention, wherein 10 single batteries are arranged between two current collecting plates, each single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode arranged in a through hole in the middle of the positive electrode frame, which are sequentially stacked, the negative electrode frame is a rectangular flat plate with a through hole in the middle, and two opposite sides of the through hole (i.e., a surface a on which a pair of opposite side edges of the rectangle are located, i.e., upper and lower sides of the surface a) on a surface a on one side of the flat plate are respectively provided with a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel with the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel with the middle through hole; the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame. The negative electrode support grid is composed of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flowing direction of the negative electrode electrolyte (more than 2 strip-shaped guide plates are sequentially arranged in parallel and at intervals from left to right). The hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 2/3 with the middle through hole parallel to the side length of the electrolyte flowing direction. Meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased. The widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 4mm, and the depth of the flow channel is 0.5 mm; the total thickness of the negative electrode frame is 1.5 mm. The width of the strip-shaped guide plate is 2mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10 mm; the thickness of the strip-shaped guide plate is 1.5 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) was the same as the thickness of the negative electrode frame. Two sides of the monocell are respectively provided with a bipolar plate, and the surface of the bipolar plate close to the negative support grid is used as a negative reaction site. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the electrode stacks and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cut-off voltage: 8V.
The coulomb efficiency of the charge and discharge of the galvanic pile is 94.2 percent, the voltage efficiency is 82.1 percent, and the energy efficiency is 77.3 percent.
Example 4
Embodiment 4 adopts the zinc-bromine single flow battery structure provided by the present invention, wherein 10 single batteries are arranged between two current collecting plates, each single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode arranged in a through hole in the middle of the positive electrode frame, which are sequentially stacked, the negative electrode frame is a rectangular flat plate with a through hole in the middle, and two opposite sides of the through hole (i.e., a surface a on which a pair of opposite side edges of the rectangle are located, i.e., upper and lower sides of the surface a) on a surface a on one side of the flat plate are respectively provided with a negative electrolyte inlet channel and a negative electrolyte outlet channel, and an electrolyte inlet distribution channel communicating the negative electrolyte inlet channel with the middle through hole, and an electrolyte outlet distribution channel communicating the negative electrolyte outlet channel with the middle through hole; the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel; a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame. The negative electrode support grid is composed of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flowing direction of the negative electrode electrolyte (more than 2 strip-shaped guide plates are sequentially arranged in parallel and at intervals from left to right). The hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 2/3 with the middle through hole parallel to the side length of the electrolyte flowing direction. Meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased. The widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 2mm, and the depth of the flow channel is 0.5 mm; the total thickness of the negative electrode frame is 1.5 mm. The width of the strip-shaped guide plate is 2mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10 mm; the thickness of the strip-shaped guide plate is 1.5 mm. The two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) is the same as the thickness of the negative electrode frame. Two sides of the monocell are respectively provided with a bipolar plate, and the surface of the bipolar plate close to the negative support grid is used as a negative reaction site. The electrolyte adopts 2mol/l zinc bromide solution, 3mol/l potassium chloride solution and 0.8mol/l MEP complexing agent. The specific electrode size, the number of the electrode stacks and the charging and discharging system are as follows:
electrode area: 800cm2。
The number of the electric pile sections: 10 section
Current density: 40mA/cm2And charging time: 1 hour, discharge cutoffVoltage stopping: 8V
The coulombic efficiency of the charge and discharge of the galvanic pile is 96.4 percent, the voltage efficiency is 82.5 percent, and the energy efficiency is 79.8 percent
Comparative example 1 adopts a traditional cathode electrode frame to assemble a battery pack of 10 cells, and it can be seen that the coulomb efficiency of the battery pack of comparative example 1 is 88.2%, the energy efficiency is 67.4%, and the efficiency and the cycle life of the battery pack are low;
comparative example 2 for a battery pack of 10 cells assembled by still using a conventional negative electrode frame, it can be seen that the coulombic efficiency of the battery pack of comparative example 2 is slightly improved, 89.1%, the energy efficiency is 70.7%, and the voltage efficiency of the battery pack is improved compared with that of comparative example 1. Mainly because the flow velocity of the electrolyte is reduced after the electrode frame is thinned, the zinc accumulated by the zinc cathode is more firmly deposited on the bipolar plate, and the capacity loss can not be caused.
In the embodiment 1, 10 batteries are assembled by adopting the negative electrode frame provided by the invention, the coulombic efficiency of the battery is 92.3%, compared with the comparative example 1 and the comparative example 2, the energy efficiency of the battery is 71.7%, and as the negative electrode frame provided by the invention is adopted, the flow rate of the negative electrolyte of the battery is greatly reduced, the deposition reliability of the zinc negative electrode is obviously improved, and the zinc formed by charging is not washed away by the electrolyte, so that more zinc reacts at the negative electrode during discharging, and the coulombic efficiency of the battery is improved;
in example 2, 10 batteries were assembled by using the negative electrode frame of the present invention, it can be seen that the coulombic efficiency of the battery can reach 93.6%, and the energy efficiency is 75%, which is greatly improved compared with example 1. The main reason is that after the cathode electrode frame is thinned, the flow rate of the electrolyte is further reduced, and the performance of the battery pack is further improved;
in embodiment 3, the negative electrode frame provided by the invention is used for assembling the battery pack, and the difference from embodiment 2 is that the hedging flow channel is 2/3 with the middle through hole parallel to the side length of the electrolyte flowing direction, so that the coulomb efficiency of the battery pack in embodiment 3 is 94.2%, the coulomb efficiency of the battery pack is slightly improved, the voltage efficiency is also improved from 80.1% to 82.1%, and the result is mainly that after the hedging flow channel is prolonged, the hedging effect of the electrolyte is improved, and the zinc deposition is more uniform;
in example 4, the cathode electrode frame provided by the present invention is adopted to assemble 10 batteries, and it can be seen that the coulomb efficiency of the battery is as high as 96.4%, and the energy efficiency is 79.8%, because the width of the cathode electrode frame runner is reduced, the electrolyte flow is further restricted, the electrolyte flow rate is greatly reduced, and the performance and reliability of the battery are improved.
In conclusion, after the cathode electrode frame provided by the invention is adopted, the performance and the reliability of the zinc-bromine single-flow battery pack are remarkably improved compared with those of a battery pack with a traditional structure.
Claims (8)
1. A zinc-bromine single flow battery structure comprises a single battery or a battery pack formed by connecting more than two single batteries in series, wherein the single battery comprises a negative electrode frame, a diaphragm and a positive carbon felt electrode which is arranged in a through hole in the middle of the positive electrode frame in a stacked mode;
the cathode electrode frame is a rectangular flat plate with a through hole in the middle, and a cathode electrolyte inlet flow channel and a cathode electrolyte outlet flow channel, an electrolyte inlet distribution flow channel communicated with the cathode electrolyte inlet flow channel and the middle through hole, and an electrolyte outlet distribution flow channel communicated with the cathode electrolyte outlet flow channel and the middle through hole are respectively arranged on two opposite sides of the through hole (namely the surface A where a pair of opposite side edges of the rectangle are positioned, namely the upper side and the lower side of the surface A) on the surface A on one side of the flat plate;
the other opposite sides of the through hole on the surface A on one side of the flat plate (namely the surface A where the other pair of opposite side edges of the rectangle are located, namely the left side and the right side of the surface A) are respectively provided with corresponding opposite flow channels which are respectively communicated with the middle through hole and the cathode electrolyte inlet flow channel;
a negative electrode support grid is arranged in the through hole in the middle of the negative electrode frame.
2. The zinc-bromine single flow battery structure of claim 1, wherein:
the negative electrolyte flows from the negative electrolyte inlet distribution flow channel to the negative electrolyte outlet distribution flow channel in the through hole, and the negative support grid consists of more than 2 strip-shaped guide plates which are arranged in parallel and at intervals along the flow direction of the negative electrolyte (the more than 2 strip-shaped guide plates are sequentially parallel and at intervals from left to right).
3. The zinc-bromine single flow battery structure of claim 1, wherein: the hedging flow channel is arranged close to the cathode electrolyte inlet distribution flow channel, is positioned at two sides (left and right sides) of the cathode electrolyte inlet distribution flow channel, and is 1/3-2/3 of the length of the side edge of the middle through hole parallel to the electrolyte flowing direction.
4. The zinc-bromine single flow battery structure of claim 1, wherein:
meanwhile, the electrolyte inlet distribution flow channel on the cathode electrode frame adopts a gradually-expanding flow channel design, namely a flow channel with the cross section area which is vertical to the flowing direction of the electrolyte and is gradually increased.
5. The zinc-bromine single flow battery structure according to claim 1 or 4, characterized in that: the widths of the negative electrolyte inlet flow channel, the negative electrolyte outlet flow channel, the negative electrolyte inlet distribution flow channel, the negative electrolyte outlet distribution flow channel and the hedging flow channel are 2mm-4mm, and the depth of the flow channel is 0.5mm-1 mm;
the total thickness of the negative electrode frame is between 1.5mm and 2 mm.
6. The zinc-bromine single flow battery structure of claim 2, wherein: the width of the strip-shaped guide plate is 2mm-4mm, and the interval between the adjacent strip-shaped guide plate or strip-shaped guide plate and the inner wall surface of the through hole which is adjacent in parallel is 10mm-15 mm;
the thickness of the strip-shaped guide plate is between 1.5mm and 2 mm.
7. The zinc-bromine single flow battery structure according to any one of claims 1 to 4, characterized in that:
the two sides of the monocell are respectively provided with a positive electrode frame and a negative electrode frame, a diaphragm is arranged between the positive electrode frame and the negative electrode frame, a positive carbon felt electrode is arranged in a middle through hole of the positive electrode frame, a negative support grid is arranged in a middle through hole of the negative electrode frame, and the negative support grid is used for supporting the diaphragm; the thickness of the grid (thickness in the direction perpendicular to the film surface) is the same as the thickness of the negative electrode frame.
8. The zinc-bromine single flow battery structure of claim 7, wherein: and polar plates or bipolar plates are respectively arranged on two sides of the monocell, and the surfaces of the polar plates or the bipolar plates close to the negative support grids are used as negative reaction sites.
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